CN105968356B - A kind of environmental protection and economy type polyarylether and preparation method thereof - Google Patents
A kind of environmental protection and economy type polyarylether and preparation method thereof Download PDFInfo
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- CN105968356B CN105968356B CN201610348248.6A CN201610348248A CN105968356B CN 105968356 B CN105968356 B CN 105968356B CN 201610348248 A CN201610348248 A CN 201610348248A CN 105968356 B CN105968356 B CN 105968356B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4018—(I) or (II) containing halogens other than as leaving group (X)
- C08G65/4025—(I) or (II) containing fluorine other than as leaving group (X)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0259—Preparatory processes metal hydrogensulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0272—Preparatory processes using other sulfur sources
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Abstract
The invention discloses a kind of environmental protection and economy type polyarylether and preparation method thereof,It is characterized in 05 parts of catalyst,0.1 100 parts of alkali,1000 3000 parts of solvents and 56 250 parts of sulfide or oxygenatedchemicals are added in reactor,Under nitrogen protection,In 150 230 DEG C of 2h of dehydration 0.5 of temperature,Reaction solution after being dehydrated,Treat that above-mentioned solution temperature is down to 80 160 DEG C of h,Add 114 467 parts of dihaloaromatic compounds,In 160 260 DEG C of 0.5 6h of reaction of temperature,In 180 280 DEG C of 0.5 10h of holding of temperature,It is cooled to 50 100 DEG C,Reaction solution is filtered,0.1 5 parts of chelating agents are added in filtrate to remove metal salt,Obtain second of filtered fluid,0.1 2 parts of flocculants are added in filtered fluid,Centrifuge the oligomer and liquid separated out,Obtain third time centrifugate；Hard resin removes the impurity in product with 48 times, every time 600 1000 parts desalted waters, dries 1 10h in 80 120 DEG C of temperature, the 0.095MPa of vacuum 0.03, obtains purifying polyarylether resin.
Description
Technical field
The present invention relates to a kind of environmental protection and economy type polyarylether and preparation method thereof, belong to Polymer Synthesizing field.
Background technology
Polyarylether mainly includes polyether sulfone (PES), polyether-ether-ketone (PEEK), polyarylether amide (PAEA), polyphenylene sulfide
(PPS), polyphenylene sulfide ketone (PASK), polyaryl thioether sulfone (PASS), aromatic polythioether amide (PASA), polyarylether thioether (PAES),
Due to its high temperature resistant, corrosion-resistant, excellent electrical property, mechanical performance and dimensional stability, it is widely used in automobile, space flight and aviation
In terms of electronic technology.Main technique and method in polyarylether industrialized production：Using auxiliary agent, sulfide or oxygenatedchemicals
HTHP solution polycondensation is carried out in polar organic solvent with dihaloaromatic compound, after reaction to used auxiliary agent and
Polar organic solvent carries out rectifying recovery so that following cycle utilizes, and this method is needed largely due to solvent during rectification and purification
Heat, energy consumption is big, cost is high, and the catalyst separation, the recovery that are related to do not only exist the problem of similar i.e. high energy consumption equally, simultaneously
Because the solubility of catalyst in a solvent is larger, so that the rate of recovery of catalyst is not high, and then polyarylether class is caused to be produced
Production cost remains high product for a long time, it is difficult to ultra-large industry amplification.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art and provides a kind of environmental protection and economy type polyarylether and its preparation side
Method, be characterized in using prepare after corresponding polyarylether use reaction filtered fluid (need not move through solvent recovery process, only need through
Simple filter is removed after insoluble matter directly as solvent use), sulfide or oxygenatedchemicals and dihaloaromatic compound be
Raw material, reacted by solution polycondensation, prepare high-performance polyarylether resin.
The purpose of the present invention is realized by following technical measures, wherein the raw material number is unless otherwise specified, it is weight
Number.
The initiation material of environmental protection and economy type polyarylether is composed of the following components：
Wherein, the structural formula of sulfide or oxygenatedchemicals is：
Na2Appointing in S or NaHS
It is a kind of；
The structural formula of dihaloaromatic compound is X-Ar-X, X=F or Cl,
At least one of,
Wherein, m=2,4,6,8,10.
The solvent is prepares the solution after the filtered removal insoluble matter of reaction solution after the polyarylether use, or is contained
Diphenyl sulphone (DPS), HMPA, N- methyl caprolactams, N, N- dimethyl propylene alkenyls urea, 1,3- dimethyl -2- imidazolines
Ketone, 1-METHYLPYRROLIDONE, quinoline, isoquinolin, sulfolane, 2,4- dimethylsulfolanes, N- cyclohexyl pyrrolidones or 2- pyrroles
Any of pyrrolidone.
The alkali be lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, barium hydroxide, aluminium hydroxide, lithium carbonate,
In sodium carbonate, potassium carbonate, magnesium carbonate, barium carbonate, lithium bicarbonate, sodium acid carbonate, saleratus, magnesium bicarbonate or barium bicarbonate
It is any.
The catalyst is lithium acetate, sodium acetate, potassium acetate, lithium benzoate, sodium benzoate, ethylenediamine tetra-acetic acid lithium, second
Sodium ethylene diamine tetracetate, sodium versenate, ethylenediamine tetra-acetic acid potassium, ethylenediamine tetra-acetic acid tripotassium, lithium chloride, sodium phosphate,
Lithium phosphate, sodium tartrate, lithium tartrate, potassium tartrate, sodium lactate, sodium sorbate, potassium sorbate, Sodium lysinate, lysine potassium,
In cystine sodium, 6-aminocaprolc acid sodium, dodecyltriethylammonium ammonium chloride, Dodecydimethylammonium bronides or odium stearate
It is at least one.
The oligomer flocculant be poly-iron chloride, polyaluminium chloride, polyiron sulfate, poly aluminium sulfate, aluminum sulfate, ferric sulfate,
It is ferrous sulfate, polysilicon acid, poly-silicic acid iron sulfate, poly- phosphorus iron chloride, poly- phosphorus aluminium chloride, ferric-polysilicate, polysulfide acid ferric-aluminum chloride, poly-
At least one of ammonium phosphate or polyacrylamide.
The chelating agent is ethylenediamine tetra-acetic acid, nitrilotriacetic acid, hydroxyacetic acid, gluconic acid, the carboxylic of diethylenetriamine five
Acid, heptonic acid, laurate, glycocholic acid, dioctyl succinate acid, ethylenediamine tetraacetic methene phosphoric acid, diethylene triamine pentamethylene phosphonic,
Appointing in the methene phosphoric acid of amine three, alginic acid, citric acid, 15- crown-s 5,18- crown-s 6, polyvinyl alcohol, polyethylene glycol or poly-dopamine
It is a kind of.
The preparation method of environmental protection and economy type polyarylether comprises the following steps：
By 0-5 part catalyst, 0.1-100 part alkali, 1000-3000 parts solvent and 56-250 parts sulfide or oxygenatedchemicals
Add in reactor, under nitrogen protection, in 150-230 DEG C of dehydration 0.5-2h of temperature, the reaction solution after being dehydrated,
When above-mentioned solution temperature is down to 80-160 DEG C, 114-467 part dihaloaromatic compounds are added, it is anti-in 160-260 DEG C of temperature
0.5-6h is answered, in 180-280 DEG C of temperature holding 0.5-10h, 50-100 DEG C is cooled to, reaction solution is filtered, and to filtering
The metal salt for adding 0.1-5 parts chelating agent while stirring in liquid afterwards to be dissolved in precipitation filtrates, then by the precipitation of precipitation
Filter off and remove, obtain second of filtered fluid, add 0.1-2 part oligomer flocculants while stirring into second of filtered fluid with heavy
Oligomer in the filtrate of shallow lake, the oligomer of precipitation and liquid are separated by the method for centrifugation, obtain third time centrifugate,
This centrifugate is directly as the solvent of polymerisation next time, and so on recycled for multiple times, without to polymerization liquid
Solvent and catalyst recovery are carried out, production is may be directly applied to and prepares polyarylether resinoid, the hard resin after reacting liquid filtering
Crude product carries out adverse current washing using the wash water of 4-8 time, each 600-1000 parts desalted water or last batch product, solid-liquid divides
From to remove the impurity wrapped up in product, the aqueous polyarylether resin after separation is in 80-120 DEG C of temperature, vacuum 0.03-
0.095MPa dries 1-10h, obtains purifying polyarylether resin；The solvent remained in resin is carried out by water-washing process simultaneously rich
Collection, subsequently to carry out the recovery of solvent in aqueous systems, by the wash water after above-mentioned solvent-rich using extraction --- rectification method reclaims
Solvent.
In environmental protection and economy type polyarylether and preparation method thereof in wash water solvent extraction --- rectification method removal process include with
Lower step：
1000 parts of above-mentioned wash water containing solvent, solvent extraction agent 1000-10000 parts are subjected to continuous extraction or extraction in extraction tower
2-6 batch-wise extraction in kettle is taken, utilizes the density contrast and solvent of extractant and the water solubility in extractant and water point
Cloth is poor, and water and solvent are separated, then by solvent-laden extraction mixed liquor in 30-90 DEG C of temperature, vacuum 0.04-
0.09MPa carries out rectification under vacuum, respectively obtains pure extractant and solvent.
The extractant is monochloro methane, dichloromethane, chloroform, carbon tetrachloride, 1,1- dichloroethanes, the chloroethenes of 1,2- bis-
Alkane, 1,1,2,2- tetrachloroethanes, hexamethylene, n-hexane, normal octane, normal heptane, toluene, dimethylbenzene, mesitylene, chlorobenzene, 1,
Any of 2,4- trichloro-benzenes or m-dichlorobenzene.
Structural characterization and performance test：
1st, the structure of polyarylether resin prepared by the present invention is confirmed through examination of infrared spectrum, as shown in Figure 1.
2nd, the glass transition temperature and fusing point of polyarylether resin are tested using differential scanning calorimetric analysis method (DSC), as a result
In detail as shown in Figure 2.
The invention has the advantages that：
1. during synthesizing polyarylene sulfide resin with dihaloaromatic compound using sulfide or oxygenatedchemicals, institute
Using the filtered fluid that most of solvent is upper secondary response, solvent recovery process is needed not move through, need to only be removed through Simple filter insoluble
Used after thing directly as solvent, avoid the rectifying recovery of a large amount of aqueous solvents in traditional handicraft, reduce solvent recovery frequency
Rate, energy consumption is reduced, and then production cost is greatly lowered.
2. because the anti-applications catalyst of polyarylether class is soluble in polar organic solvent used in polymerisation, so that
Prepare containing catalyst needed for substantial amounts of polymerization in the reaction filtered fluid after corresponding polyarylether use, and then cause except for the first time
Preparing polyarylether resin needs to add outside larger amount of catalyst, and other use the reaction filtered fluid after use to prepare polyarylether
Or very small amount catalyst need not need to be only added during product, so as to reduce its production cost.
Metal salt in filtered fluid is removed 3. being respectively facilitated in this method using chelating agent and oligomer flocculant (especially
That great heavy metallic salt such as molysite, manganese salt and lead salt etc. are influenceed on polymerisation) and low molecule amount sulfide (especially to gathering
Close the cyclic oligomer that reaction has great deterioration to influence) so that the filtered fluid purity after use is higher, advantageously in next
The polymerization of batch products, further optimizes polymerisation, its have security it is good, it is repeated it is strong, molecular weight is high, high income
A little.
4. due to cleaning product, the processing method of the caused wash water containing solvent is the work of rectifying after first extracting in this method
Skill, used extractant are the less organic solvent of specific heat, are easier to separate with solvent, and more traditional polyarylether resinoid closes
Into method for recovering solvents (due to the water of a large amount of high specific heat, while only with single rectification process, cause its energy consumption high) energy consumption
It is low.
Brief description of the drawings：
Fig. 1 is polyarylene sulfide resin infrared spectrogram
(1) it is the infrared spectrogram of polyphenylene sulfide
(2) it is the infrared spectrogram of polyarylene sulfide ketone
(3) it is the infrared spectrogram of half aromatics polyphenylene sulfide acid amides
Fig. 2 is polyarylene sulfide resin differential scanning calorimetric analysis curve
(1) it is the differential scanning calorimetric analysis curve of polyphenylene sulfide
(2) it is the differential scanning calorimetric analysis curve of polyarylene sulfide ketone
(3) it is the differential scanning calorimetric analysis curve of half aromatics polyphenylene sulfide acid amides
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that the present embodiment is served only for
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made according to the content of the invention described above.
Embodiment 1
By 1kg lithium acetates, 0.1kg sodium hydroxides, the 500kg last times prepare the reaction filtered fluid after polyphenylene sulfide use
The vulcanized sodium 130kg that (HMPA and catalyst mixed solution) and water content are 40% is added in reactor, in nitrogen
Under gas shielded, in 200 DEG C of dehydration 2h of temperature, the reaction solution after being dehydrated, treat that above-mentioned solution temperature is down to 160 DEG C
When, 147kg paracide is added, in 230 DEG C of reaction 3h of temperature, in 265 DEG C of holding 1h of temperature, 90 DEG C are cooled to, by reaction solution
Filtered, 0.1kg18- 6 metal salts to be dissolved in precipitation filtrates of crown- are added into the liquid after filtering, then will be separated out
Precipitation filter off and remove, obtain second of filtered fluid, 0.1kg poly-iron chlorides added in second of filtered fluid with precipitation filtrates
Oligomer, the oligomer of precipitation and liquid are separated by the method for centrifugation, obtain third time centrifugate, this centrifugate
By directly as the solvent of polymerisation next time；And the hard resin crude product after reacting liquid filtering using 6 times, every time
The wash water of 1000kg last batch products carries out adverse current washing, separation of solid and liquid, to remove the impurity wrapped up in product, after separation
Aqueous polyphenylene sulfide dries 6h in 80 DEG C of temperature, vacuum 0.085MPa, obtains purifying polyphenylene sulfide.Its yield is
94.6%, intrinsic viscosity=0.32 (viscosity test solvent is 1- naphthalene chlorides), IR Characterization in detail as shown in Figure 1, dsc analysis
As shown in Figure 2：Its fusing point is 293 DEG C；By the wash water after above-mentioned solvent-rich using extraction --- rectification method recycling design：Will be upper
The 1000kg of wash water containing solvent, dichloromethane 2000kg continuous extractions in extraction tower are stated, water and solvent are separated, then will contain
The extraction mixed liquor of solvent carries out rectification under vacuum in 30 DEG C of temperature, vacuum 0.06MPa, respectively obtains pure hexamethylene and six
The rate of recovery of methyl phosphoric triamide, solvent (HMPA) and extractant (hexamethylene) is respectively 94.7%, 96.0%.
Embodiment 2
By 0.2kg sodium tartrates, 5kg potassium hydroxide, the 1200kg last times prepare the reaction after polyphenylene sulfide ketone use
Filtered fluid (N- cyclohexyl pyrrolidones and catalyst mixed solution) and the NaHS 82.4kg that water content is 32% add anti-
Answer in kettle, under nitrogen protection, in 185 DEG C of dehydration 1.5h of temperature, the reaction solution after being dehydrated, treat above-mentioned solution temperature
When degree is down to 160 DEG C, 218kg 4 is added, 4 '-difluoro benzophenone, in 205 DEG C of reaction 2h of temperature, 270 DEG C keep in temperature
3h, 100 DEG C are cooled to, reaction solution is filtered, 0.1kg polyvinyl alcohol is added in liquid after filtration with precipitation filtrates
The metal salt of dissolving, then the precipitation of precipitation is filtered off and removed, obtains second of filtered fluid, is added into second of filtered fluid
0.2kg APPs are separated the oligomer of precipitation and liquid by the method for centrifugation with the oligomer in precipitation filtrates,
Third time centrifugate is obtained, this centrifugate is by directly as the solvent of polymerisation next time；And consolidating after reacting liquid filtering
Body resin crude product carries out adverse current washing, separation of solid and liquid using 6 times, each 1000kg desalted waters, to remove what is wrapped up in product
Impurity, the aqueous polyphenylene sulfide after separation dry 6h in 80 DEG C of temperature, vacuum 0.085MPa, obtain purifying polyphenylene sulfide
Ketone resin.Its yield is 92.4%, and intrinsic viscosity=1.08 (viscosity test solvent is the concentrated sulfuric acid), IR Characterization refers to Fig. 1
Shown, dsc analysis is as shown in Figure 2：Its fusing point is 347.5 DEG C；By the wash water after above-mentioned solvent-rich using extraction --- rectification method
Recycling design：By the above-mentioned 1000kg of wash water containing solvent, chlorobenzene 2000kg continuous extractions in extraction tower, water and solvent are divided
From, then by it is solvent-laden extraction mixed liquor 80 DEG C of temperature, vacuum 0.08MPa carry out rectification under vacuum, respectively obtain pure
The rate of recovery of chlorobenzene and N- cyclohexyl pyrrolidones, solvent (N- cyclohexyl pyrrolidones) and extractant (chlorobenzene) is respectively
94.2%th, 95.6%.
Embodiment 3
By 0.5kg lithium phosphates, 12kg magnesium hydroxides, after 1800kg half aromatics polyphenylene sulfide acid amides uses of last preparation
Reaction filtered fluid (N- methyl caprolactams and catalyst mixed solution) and vulcanized sodium 130kg that water content is 40% add it is anti-
Answer in kettle, under nitrogen protection, in 195 DEG C of dehydration 2h of temperature, the reaction solution after being dehydrated, treat above-mentioned solution temperature
When being down to 120 DEG C, 360kg 1 is added, double (4- fluorobenzoyls) hexamethylene diamines of 6-, in 200 DEG C of reaction 2h of temperature, in 235 DEG C of temperature
6h is kept, 90 DEG C is cooled to, reaction solution is filtered, 0.5kg poly-dopamines are added in liquid after filtration to precipitate filter
The metal salt dissolved in liquid, then the precipitation of precipitation is filtered off and removed, obtains second of filtered fluid, added into second of filtered fluid
Enter 0.1kg polyacrylamides with the oligomer in precipitation filtrates, carried out the oligomer of precipitation and liquid by the method for centrifugation
Separation, obtains third time centrifugate, this centrifugate is by directly as the solvent of polymerisation next time；And after reacting liquid filtering
Hard resin crude product adverse current washing, separation of solid and liquid are carried out using 5 times, the wash water of each 600kg last batches product, to go
Except the impurity wrapped up in product, the aqueous half aromatics polyphenylene sulfide amide resin after separation is in 90 DEG C of temperature, vacuum 0.07MPa
8h is dried, obtains half aromatics polyphenylene sulfide amide resin of purifying.Its yield is 93.6%, and (viscosity is surveyed for intrinsic viscosity=0.63
Examination solvent is the concentrated sulfuric acid), in detail as shown in Figure 1, dsc analysis is as shown in Figure 2 for IR Characterization：Its fusing point is 302,315 DEG C；Will be above-mentioned
Wash water after solvent-rich is using extraction --- rectification method recycling design：The above-mentioned 1000kg of wash water containing solvent, chloroform 1000kg are existed
3 batch-wise extractions are carried out in extraction kettle, water and solvent are separated, then by solvent-laden extraction mixed liquor in temperature 35
DEG C, vacuum 0.05MPa carry out rectification under vacuum, respectively obtain pure chloroform and N- methyl caprolactams, solvent (N- methyl oneself
Lactams) and the rate of recovery of extractant (chloroform) be respectively 95.7%, 98.8%.
Embodiment 4
By 1kg sodium ethylene diamine tetracetates, 100kg potassium carbonate, the 1000kg last times prepare anti-after polyether-ether-ketone use
Answer filtered fluid (HMPA and catalyst mixed solution) and 110kg hydroquinones to add in reactor, protected in nitrogen
Under shield, in 180 DEG C of dehydration 2h of temperature, the reaction solution after being dehydrated, when above-mentioned solution temperature is down to 80 DEG C, then add
Enter 218kg 4,4 '-difluoro benzophenone, in 200 DEG C of reaction 3h of temperature, in 280 DEG C of holding 4h of temperature, be cooled to 100 DEG C, will
Reaction solution is filtered, and metal salt of the 5kg nitrilotriacetic acids to be dissolved in precipitation filtrates is added into the liquid after filtering, then
The precipitation of precipitation is filtered off and removed, obtains second of filtered fluid, in second of filtered fluid add 2kg polysulfide acid ferric-aluminum chlorides with
Oligomer in precipitation filtrates, the oligomer of precipitation and liquid are separated by the method for centrifugation, obtain third time and centrifuge
Liquid, this centrifugate is by directly as the solvent of polymerisation next time；And the hard resin crude product after reacting liquid filtering is adopted
Adverse current washing, separation of solid and liquid are carried out with 4 times, each 1000kg desalted waters, to remove the impurity wrapped up in product, containing after separation
Water polyether-ether-ketone resin dries 10h in 80 DEG C of temperature, vacuum 0.085MPa, obtains purifying polyether-ether-ketone resin.Its yield is
93.1%, intrinsic viscosity=0.96 (viscosity test solvent is the concentrated sulfuric acid)；By the wash water after above-mentioned solvent-rich using extraction
Take --- rectification method recycling design：By the above-mentioned 1000kg of wash water containing solvent, dichloromethane 2000kg continuous extractions in extraction tower,
Water and solvent are separated, then solvent-laden extraction mixed liquor is subjected to decompression essence in 30 DEG C of temperature, vacuum 0.06MPa
Evaporate, respectively obtain pure dichloromethane and HMPA, solvent (HMPA) and extractant (dichloromethane
Alkane) the rate of recovery be respectively 96.1%, 98.5%.
Embodiment 5
By 60kg sodium carbonate, the 3000kg last times prepare reaction filtered fluid (the N- methyl pyrroles after polyphenylene oxide sulfide use
Pyrrolidone and catalyst mixed solution) and 110kg resorcinols add in reactor, it is under nitrogen protection, de- in 190 DEG C of temperature
Water reacts 1h, the reaction solution after being dehydrated, when above-mentioned solution temperature is down to 120 DEG C, adds 255kg 4,4 '-dichloro two
Diphenyl sulfide, in 220 DEG C of reaction 1.5h of temperature, in 260 DEG C of holding 6h of temperature, 80 DEG C are cooled to, reaction solution is filtered, to mistake
Metal salt of the 2kg dioctyl succinates acid to be dissolved in precipitation filtrates is added in liquid after filter, then filters the precipitation of precipitation
Remove, obtain second of filtered fluid, the poly- phosphorus aluminium chloride of 0.2kg is added in second of filtered fluid with oligomeric in precipitation filtrates
Thing, the oligomer of precipitation and liquid are separated by the method for centrifugation, obtain third time centrifugate, this centrifugate will be direct
Solvent as polymerisation next time；And the hard resin crude product after reacting liquid filtering is using on 5 times, each 800kg
The wash water of one batch products carries out adverse current washing, separation of solid and liquid, to remove the impurity wrapped up in product, the aqueous polyphenyl after separation
Ether thioether resin dries 6h in 100 DEG C of temperature, vacuum 0.09MPa, obtains purifying polyphenylene oxide sulfide resin.Its yield is
94.2%, intrinsic viscosity=0.68 (viscosity test solvent is the concentrated sulfuric acid)；By the wash water after above-mentioned solvent-rich using extraction
Take --- rectification method recycling design：The above-mentioned 1000kg of wash water containing solvent, 1,2- dichloroethanes 1000kg are carried out 3 in extraction kettle
Secondary batch-wise extraction, water and solvent are separated, then by solvent-laden extraction mixed liquor in 40 DEG C of temperature, vacuum
0.08MPa carries out rectification under vacuum, respectively obtains pure 1,2- dichloroethanes and 1-METHYLPYRROLIDONE, solvent (N- methyl pyrroles
Pyrrolidone) and the rate of recovery of extractant (1,2- dichloroethanes) be respectively 96.3%, 97.2%.
Embodiment 6
By 20kg sodium hydroxides, the 2500kg last times prepare the reaction filtered fluid (1,3- after poly biphenyl ether acid amides use
Dimethyl-2-imidazolinone and catalyst mixed solution) and 186kg '-biphenyl diphenols add reactor in, under nitrogen protection, in
195 DEG C of dehydration 0.5h of temperature, the reaction solution after being dehydrated, when above-mentioned solution temperature is down to 140 DEG C, add
Double (4- fluorobenzoyls) phenylenediamines of 352kg1,4-, in 200 DEG C of reaction 6h of temperature, in 230 DEG C of holding 10h of temperature, it is cooled to 60
DEG C, reaction solution is filtered, gold of the methene phosphoric acid of 0.5kg amine three to be dissolved in precipitation filtrates is added into the liquid after filtering
Belong to salt, then the precipitation of precipitation is filtered off and removed, obtains second of filtered fluid, the poly- silicon of 0.1kg is added in second of filtered fluid
The oligomer of precipitation and liquid are separated, obtained with the oligomer in precipitation filtrates by sour ferric sulfate by the method for centrifugation
Third time centrifugate, this centrifugate is by directly as the solvent of polymerisation next time；And the solid tree after reacting liquid filtering
Fat crude product carries out adverse current washing, separation of solid and liquid using 6 times, each 700kg desalted waters, to remove the impurity wrapped up in product,
Aqueous poly biphenyl ether amide resin after separation dries 6h in 110 DEG C of temperature, vacuum 0.095MPa, obtains purifying poly biphenyl ether
Amide resin.Its yield is 92.2%, intrinsic viscosity=0.82 (viscosity test solvent is the concentrated sulfuric acid)；Above-mentioned enrichment is molten
Wash water after agent is using extraction --- rectification method recycling design：By the above-mentioned 1000kg of wash water containing solvent, chloroform 5000kg in extraction tower
Interior continuous extraction, water and solvent are separated, then by solvent-laden extraction mixed liquor in 35 DEG C of temperature, vacuum 0.05MPa
Rectification under vacuum is carried out, respectively obtains pure chloroform and DMI, solvent (1,3- dimethyl -2- imidazoles
Quinoline ketone) and the rate of recovery of extractant (chloroform) be respectively 98.0%, 99.1%.
Embodiment 7
By 10kg sodium hydroxides, the 2500kg last times prepare reaction filtered fluid (the N- methyl pyrroles after polyphenylene sulfide use
Pyrrolidone and catalyst mixed solution) and 56kg NaHSs add in reactor, it is under nitrogen protection, de- in 185 DEG C of temperature
Water reacts 1h, and the reaction solution after be dehydrated, when above-mentioned solution temperature is down to 120 DEG C, 114kg is to difluorobenzene for addition,
210 DEG C of reaction 2h of temperature, in 265 DEG C of holding 4h of temperature, 80 DEG C are cooled to, reaction solution is filtered, to the liquid after filtering
Metal salt of the middle addition 1kg diethylene triamine pentamethylene phosphonics to be dissolved in precipitation filtrates, then filters off the precipitation of precipitation
Remove, obtain second of filtered fluid, 0.3kg polysulfide acid ferric-aluminum chlorides are added in second of filtered fluid with oligomeric in precipitation filtrates
Thing, the oligomer of precipitation and liquid are separated by the method for centrifugation, obtain third time centrifugate, this centrifugate will be direct
Solvent as polymerisation next time；And the hard resin crude product after reacting liquid filtering is using on 6 times, each 1000kg
The wash water of one batch products carries out adverse current washing, separation of solid and liquid, to remove the impurity wrapped up in product, the aqueous polyphenyl after separation
Sulfide resin dries 6h in 100 DEG C of temperature, vacuum 0.09MPa, obtains purifying polyphenylene sulfide.Its yield is 92.2%,
Intrinsic viscosity=0.29 (viscosity test solvent is 1- naphthalene chlorides)；By the wash water after above-mentioned solvent-rich using extraction --- essence
Evaporate method recycling design：The above-mentioned 1000kg of wash water containing solvent, 1,2- dichloroethanes 1000kg are subjected to 3 batch (-type)s in extraction kettle
Extraction, water and solvent are separated, then solvent-laden extraction mixed liquor is subtracted in 40 DEG C of temperature, vacuum 0.08MPa
Rectifying is pressed, respectively obtains pure 1,2- dichloroethanes and 1-METHYLPYRROLIDONE, solvent (1-METHYLPYRROLIDONE) and extraction
The rate of recovery of agent (1,2- dichloroethanes) is respectively 95.8%, 98.1%.
Embodiment 8
By 5kg lithium acetates, 100kg potassium carbonate, the 2800kg last times prepare the reaction filtering after polyarylene sulfide ketone use
Liquid (1,3- dimethyl-2-imidazolinones and catalyst mixed solution) and 250kg4,4 '-dimercapto diphenyl sulfide add reactor
In, under nitrogen protection, in 220 DEG C of dehydration 1.5h of temperature, the reaction solution after being dehydrated, treat above-mentioned solution temperature drop
During to 150 DEG C, 467kg Isosorbide-5-Nitraes-bis- (4- chlorobenzenes thioethers) benzophenone is added, in 220 DEG C of reaction 3h of temperature, in 280 DEG C of temperature
6h is kept, 90 DEG C is cooled to, reaction solution is filtered, 0.5kg polyvinyl alcohol is added into the liquid after filtering to precipitate filter
The metal salt dissolved in liquid, then the precipitation of precipitation is filtered off and removed, obtains second of filtered fluid, added in second of filtered fluid
Enter 0.1kg polyacrylamides with the oligomer in precipitation filtrates, carried out the oligomer of precipitation and liquid by the method for centrifugation
Separation, obtains third time centrifugate, this centrifugate is by directly as the solvent of polymerisation next time；And after reacting liquid filtering
Hard resin crude product adverse current washing, separation of solid and liquid are carried out using 7 times, each 900kg desalted waters, wrapped up with removing in product
Impurity, aqueous poly arylidene thio-ester ketone resin after separation dries 5h in 110 DEG C of temperature, vacuum 0.095MPa, it is poly- to obtain purifying
Arylene sulfide ketone resin.Its yield is 89.2%, intrinsic viscosity=0.57 (viscosity test solvent is the concentrated sulfuric acid)；By above-mentioned richness
Collect the wash water after solvent using extraction --- rectification method recycling design：The above-mentioned 1000kg of wash water containing solvent, chloroform 5000kg are being extracted
Continuous extraction in tower is taken, water and solvent are separated, then by solvent-laden extraction mixed liquor in 35 DEG C of temperature, vacuum
0.05MPa carries out rectification under vacuum, respectively obtains pure chloroform and DMI, solvent (1,3- diformazan
Base -2- imidazolones) and the rate of recovery of extractant (chloroform) be respectively 95.0%, 97.6%.
Claims (9)
1. a kind of environmental protection and economy type polyarylether, it is characterised in that the initiation material of the polyarylether is composed of the following components, by weight
It is calculated as：
Wherein, the structural formula of sulfide or oxygenatedchemicals is：
Na2Any of S or NaHS；
The structural formula of dihaloaromatic compound is X-Ar-X, X=F or Cl,
At least one of,
Wherein, m=2,4,6,8,10；
The environmental protection and economy type polyarylether is made using following preparation methods：
0-5 part catalyst, 0.1-100 part alkali, 1000-3000 parts solvent and 56-250 parts sulfide or oxygenatedchemicals are added
In reactor, under nitrogen protection, in 150-230 DEG C of dehydration 0.5-2h of temperature, the reaction solution after being dehydrated, treat
When stating solution temperature and being down to 80-160 DEG C, 114-467 part dihaloaromatic compounds are added, in 160-260 DEG C of reaction of temperature
0.5-6h, then in 180-280 DEG C of temperature holding 0.5-10h, be cooled to 50-100 DEG C, reaction solution is filtered, and to filtering
The metal salt for adding 0.1-5 parts chelating agent while stirring in liquid afterwards to be dissolved in precipitation filtrates, then by the precipitation of precipitation
Filter off and remove, obtain second of filtered fluid, add 0.1-2 part oligomer flocculants while stirring into second of filtered fluid with heavy
Oligomer in the filtrate of shallow lake, the oligomer of precipitation and liquid are separated by the method for centrifugation, obtain third time centrifugate,
This centrifugate is directly as the solvent of polymerisation next time, and so on recycled for multiple times, without to polymerization liquid
Solvent and catalyst recovery are carried out, production is may be directly applied to and prepares polyarylether resinoid, the hard resin after reacting liquid filtering
Crude product carries out adverse current washing using the wash water of 4-8 time, each 600-1000 parts desalted water or last batch product, solid-liquid divides
From to remove the impurity wrapped up in product, the aqueous polyarylether resin after separation is in 80-120 DEG C of temperature, vacuum 0.03-
0.095MPa dries 1-10h, obtains purifying polyarylether resin；The solvent remained in resin is carried out by water-washing process simultaneously rich
Collection, subsequently to carry out the recovery of solvent in aqueous systems, by the wash water after above-mentioned solvent-rich using extraction --- rectification method reclaims
Solvent.
2. according to environmental protection and economy type polyarylether described in claim 1, it is characterised in that after solvent is prepares the polyarylether use
Reaction solution it is filtered remove insoluble matter after solution, or containing diphenyl sulphone (DPS), HMPA, N- methyl caprolactams,
N, N- dimethyl propylene alkenyl urea, 1,3- dimethyl-2-imidazolinones, 1-METHYLPYRROLIDONE, quinoline, isoquinolin, sulfolane, 2,
Any of 4- dimethylsulfolanes, N- cyclohexyl pyrrolidones or 2-Pyrrolidone.
3. according to environmental protection and economy type polyarylether described in claim 1, it is characterised in that alkali is lithium hydroxide, sodium hydroxide, hydrogen-oxygen
Change potassium, magnesium hydroxide, barium hydroxide, aluminium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, barium carbonate, lithium bicarbonate,
Any of sodium acid carbonate, saleratus, magnesium bicarbonate or barium bicarbonate.
4. according to environmental protection and economy type polyarylether described in claim 1, it is characterised in that catalyst is lithium acetate, sodium acetate, acetic acid
Potassium, lithium benzoate, sodium benzoate, ethylenediamine tetra-acetic acid lithium, sodium ethylene diamine tetracetate, sodium versenate, ethylenediamine tetraacetic
Potassium acetate, ethylenediamine tetra-acetic acid tripotassium, lithium chloride, sodium phosphate, lithium phosphate, sodium tartrate, lithium tartrate, potassium tartrate, lactic acid
Sodium, sodium sorbate, potassium sorbate, Sodium lysinate, lysine potassium, cystine sodium, 6-aminocaprolc acid sodium, dodecyltriethylammonium chlorine
Change at least one of ammonium, Dodecydimethylammonium bronides or odium stearate.
5. according to environmental protection and economy type polyarylether described in claim 1, it is characterised in that oligomer flocculant is poly-iron chloride, gathered
Aluminium chloride, polyiron sulfate, poly aluminium sulfate, aluminum sulfate, ferric sulfate, ferrous sulfate, polysilicon acid, poly-silicic acid iron sulfate, poly- phosphorus chlorination
At least one of iron, poly- phosphorus aluminium chloride, ferric-polysilicate, polysulfide acid ferric-aluminum chloride, APP or polyacrylamide.
6. according to environmental protection and economy type polyarylether described in claim 1, it is characterised in that chelating agent is ethylenediamine tetra-acetic acid, nitrilo
Triacetic acid, hydroxyacetic acid, gluconic acid, diethylenetriamine pentacarboxylic acid, heptonic acid, laurate, glycocholic acid, dioctyl succinate acid,
Ethylenediamine tetraacetic methene phosphoric acid, diethylene triamine pentamethylene phosphonic, alginic acid, citric acid, 15- crown-s 5,18- crown-s 6, polyvinyl alcohol,
Any of polyethylene glycol or poly-dopamine.
7. according to the preparation method of one of claim 1~6 environmental protection and economy type polyarylether, it is characterised in that this method bag
Include following steps：
0-5 part catalyst, 0.1-100 part alkali, 1000-3000 parts solvent and 56-250 parts sulfide or oxygenatedchemicals are added
In reactor, under nitrogen protection, in 150-230 DEG C of dehydration 0.5-2h of temperature, the reaction solution after being dehydrated, treat
When stating solution temperature and being down to 80-160 DEG C, 114-467 part dihaloaromatic compounds are added, in 160-260 DEG C of reaction of temperature
0.5-6h, then in 180-280 DEG C of temperature holding 0.5-10h, be cooled to 50-100 DEG C, reaction solution is filtered, and to filtering
The metal salt for adding 0.1-5 parts chelating agent while stirring in liquid afterwards to be dissolved in precipitation filtrates, then by the precipitation of precipitation
Filter off and remove, obtain second of filtered fluid, add 0.1-2 part oligomer flocculants while stirring into second of filtered fluid with heavy
Oligomer in the filtrate of shallow lake, the oligomer of precipitation and liquid are separated by the method for centrifugation, obtain third time centrifugate,
This centrifugate is directly as the solvent of polymerisation next time, and so on recycled for multiple times, without to polymerization liquid
Solvent and catalyst recovery are carried out, production is may be directly applied to and prepares polyarylether resinoid, the hard resin after reacting liquid filtering
Crude product carries out adverse current washing using the wash water of 4-8 time, each 600-1000 parts desalted water or last batch product, solid-liquid divides
From to remove the impurity wrapped up in product, the aqueous polyarylether resin after separation is in 80-120 DEG C of temperature, vacuum 0.03-
0.095MPa dries 1-10h, obtains purifying polyarylether resin；The solvent remained in resin is carried out by water-washing process simultaneously rich
Collection, subsequently to carry out the recovery of solvent in aqueous systems, by the wash water after above-mentioned solvent-rich using extraction --- rectification method reclaims
Solvent.
8. according to the preparation method of environmental protection and economy type polyarylether described in claim 7, it is characterised in that molten in wash water in this method
The extraction of agent --- rectification method removal process comprises the following steps：
1000 parts of above-mentioned wash water containing solvent, solvent extraction agent 1000-10000 parts are subjected to continuous extraction or extraction kettle in extraction tower
Interior 2-6 batch-wise extraction, it is poor using solubility distribution of the density contrast and solvent of extractant and water in extractant and water,
Water and solvent are separated, then solvent-laden extraction mixed liquor is carried out in 30-90 DEG C of temperature, vacuum 0.04-0.09MPa
Rectification under vacuum, respectively obtain pure extractant and solvent.
9. according to the preparation method of environmental protection and economy type polyarylether described in claim 8, it is characterised in that included in this method wash water
Solvent recovery process employed in extractant for monochloro methane, dichloromethane, chloroform, carbon tetrachloride, 1,1- dichloroethanes,
1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes, hexamethylene, n-hexane, normal octane, normal heptane, toluene, dimethylbenzene, equal front three
Any of benzene, chlorobenzene, 1,2,4- trichloro-benzenes or m-dichlorobenzene.
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